Recent development in direct methods for trifluoromethylthiolation
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1 Recent development in direct methods for trifluoromethylthiolation Organic Seminar Zeren Zhang Dec 4 th,
2 Outline 1. Introduction 2. Direct trifluoromethylthiolation Electrophilic trifluoromethylthiolation Transition metal-catalyzed nucleophilic trifluoromethylthiolation 3. Summary 2
3 Introduction Coccidiosis 3
4 Boiko, V. N., Beilstein. J Org Chem, 2010, 6,
5 Introduction Potential Inhibitor of Cholesteryl Ester Transfer Protein Inhibitor R IC 50 (μm) in buffer 1 OMe 15 2 OEt OPh OCF SCF Durley, R.C., et al, J. Med. Chem., 2002, 45,
6 Introduction Element H Be B C N F Cl Br Radius (pm) Gianotti., A,J; Tower, P.A. Sheley, J.H, Conte, P.A, Spiro,C, Ferro, A.J., Fitchen, J.H, Riscoe, M.K; J Biol Chem, 1990, 265,
7 Introduction Hansch constant (π), a number to present lipophilic properties. substituent π substituent π X = H 0.00 X= CH X = F 0.14 X= CF X = Cl 0.71 X= OCF X = Br 0.86 X= SCF X = I 1.12 X= CH(CH 3 ) Lipophilicity Increments π as Assessed for Monosubstituted Benzenes H 5 C 6 -X Lipophilic compounds have a tendency to be oxidized by liver enzymes. 7 Hansch, C,. Leo, A,. Unger, S.H,. Kim, K.H, Xikaitani, D and Lien, EJ, J. Med. Chem., 1973, 16 (11), 1207
8 Introduction Bohm, H. J.; Banner, D.; Bendels, S.; Kansy, M.; Kuhn, B.; Muller, K.; Obst-Sander, U.; Stahl, M., Chembiochem 2004, 5,
9 Introduction Important intermediate for the synthesis of trifluoromethyl sulfones and sulfoxides Ancel, JE., Vidal, J., US patent B2, Jan. 29,
10 Previous Indirect methods Substitution of halogen atoms by fluorine Corrosive Low boiling point of HF (19.4 ) Pre-purification of SbF 3 - sublimation 10 Scherer, B., Angew. Chem, 1939,
11 Previous Indirect methods Trifluoromethylation Long synthesis steps 11 Umemoto, T., Ishihara, S., J. Am. Chem. Soc. 1993, 115,
12 Previous Indirect methods Trifluoromethylation R Yield (%) m-br 82 p-no 2 88 o-nh 2 82 m-nh 2 72 Its impact sensitiveness is similar to that of TNT. And highly explosive to heat. Eisenerger, P., Gischig, S., Togni, A., Chem. Eur. J, 2006, 12, Fiederling, N., Haller, J., Schramm, H., Org. Process Res. Dev. 2013, 17,
13 Previous Indirect methods Radical reaction 4-NHCO 2 CH 3 70% 9% 2-NH 2 66% 7% 4-NO 2 24% Disulfide bond formation Must be performed in Liquid NH 3 Low yield for some substituents 13 Wakselman, C., Tordeux, M., Chem. Comm., 1984,
14 Outline 1. Introduction 2. Direct trifluoromethylthiolation Electrophilic trifluoromethylthiolation Transition metal-catalyzed nucleophilic trifluoromethylthiolation 3. Summary 14
15 Direct trifluoromethylthiolation Electrophilic method Cl-SCF 3 Nucleophilic method Ag-SCF 3 15
16 Electrophilic methods R must be an electron-donating group Croft, T,S., Phosphorus Sulfur Relat. Elem, 1976, 2, Gerstenberger, M, R,C., Hass, A, J., J. Fluorine. Chem. 1983, 23,
17 Sheppard, W.A., J. Org, Chem, 1964, 29,
18 Electrophilic methods Hypervalent Iodine reagent Trifluoromethanesulfenamide Trifluoromethanesulfonyl hypervalent iodonium ylide (iodonium ylide) 18
19 Hypervalent Iodine reagent 19 Shao, X.; Wang, X.; Yang, T.; Lu, L.; Shen, Q., Angew. Chem. Int. Ed, 2013, 52,
20 Hypervalent Iodine reagent Stereoselective introduction of SCF 3 groups to generate chiral centers to beta-ketoesters Substitution (R) H 2-Me 4-OMe 2,3-diOMe 3-Cl 2-Br 3-Br 4-Br Yield (%) ee (%) Wang, X.; Yang, T.; Cheng, X.; Shen, Q., Angew. Chem. Int. Ed, 2013,
21 Hypervalent Iodine reagent 21 Wang, X.; Yang, T.; Cheng, X.; Shen, Q., Angew. Chem. Int. Ed, 2013,
22 Hypervalent Iodine reagent Catalyst Yield (%) ee (%) (R) (S) 3 <5 N/A 22 Wang, X.; Yang, T.; Cheng, X.; Shen, Q., Angew. Chem. Int. Ed, 2013,
23 Hypervalent Iodine reagent 23 Lee, J.-H.; Yoo, M.-S.; Jung, J.-H.; Jew, S.-s.; Park, H.-g.; Jeong, B.-S., Tetrahedron 2007, 63, Wang, X.; Yang, T.; Cheng, X.; Shen, Q., Angew. Chem. Int. Ed, 2013,
24 Hypervalent Iodine reagent 24 Wang, X.; Yang, T.; Cheng, X.; Shen, Q., Angew. Chem. Int. Ed, 2013,
25 Electrophilic methods Hypervalent Iodine reagent Trifluoromethanesulfenamide Trifluoromethanesulfonyl hypervalent iodonium ylide 26
26 Trifluoromethanesulfenamide A New SCF 3 source: Found as a sideproduct of prepareing Trifluoromethanesulfinamidines Ferry,A.; Billard, T.; Langlois, B. R.; Bacque, E.;. J. Org. Chem. 2008, 73,
27 Trifluoromethanesulfenamide 28 Ferry,A.; Billard, T.; Langlois, B. R.; Bacque, E.;. J. Org. Chem. 2008, 73,
28 Trifluoromethanesulfenamide Apply to various primary and secondary amines Ferry,A.; Billard, T.; Langlois, B. R.; Bacque, E, J. Org. Chem. 2008, 73, Ferry, A.; Billard, T.; Bacqué, E.; Langlois, B. R., J Fluorine Chem 2012, 134,
29 Trifluoromethanesulfenamide Then apply to alkenes and alkynes 30 Ferry, A.; Billard, T.; Langlois, B. R.; Bacque, E. Angew. Chem. Int. Ed 2009, 48,
30 Trifluoromethanesulfenamide 31 Ferry, A.; Billard, T.; Langlois, B. R.; Bacque, E. Angew. Chem. Int. Ed 2009, 48,
31 Trifluoromethanesulfenamide 32 Ferry, A.; Billard, T.; Langlois, B. R.; Bacque, E. Angew. Chem. Int. Ed 2009, 48,
32 Trifluoromethanesulfenamide Intramolecular cyclization 33 Xiao, Q.; Sheng, J.; Chen, Z.; Wu, J.. Chem Comm, 2013, 49,
33 Trifluoromethanesulfenamide synthesize SCF 3 contained pyrrolidinoindoline derivates Entry Acid Temp ( ) Time (h) ratio Isolated yield 1 TsOH : TsOH rt 12 >20: (+)-CSA rt 12 >20: MsOH rt 12 9: HOAc rt 24 NR NR 6 CF 3 COOH rt : BF 3 -OEt 2 rt 48 Nearly only 1b Yang, Y.; Jiang, X.; Qing, F. L., J. Org. Chem 2012, 77,
34 Trifluoromethanesulfenamide Drawback 1 Drawback 2 Ferry, A.; Billard, T.; Langlois, B. R.; Bacque, E. Angew. Chem. Int. Ed 2009, 48, Liu, J., Chu, L., and Qing, FL., Org. Lett., 2013, 15,
35 Trifluoromethanesulfenamide Acid BF 3 Et 2 O TsOH CH 3 COCl CH 3 COCl CH 3 COCl Solvent DCM DCM DCM DMF DMAC Yield (%) Liu, J., Chu, L., and Qing, FL., Org. Lett., 2013, 15,
36 Trifluoromethanesulfenamide Extension to Grignard reagent & terminal alkynes 37 Baert, F.; Colomb, J.; Billard, T., Angew. Chem. Int. Ed 2012, 51,
37 Trifluoromethanesulfenamide 38 Alazet, S.; Zimmer, L.; Billard, T., Angew. Chem. Int. Ed ,
38 Electrophilic methods Hypervalent Iodine reagent Trifluoromethanesulfenamide Trifluoromethanesulfonyl hypervalent iodonium ylide 39
39 Iodonium Ylide Yang, Y. D.; Azuma, A.; Tokunaga, E.; Yamasaki, M.; Shiro, M.; Shibata, N., J. Am. Chem. Soc. 2013, 135,
40 Iodonium Ylide 41 Yang, Y. D.; Azuma, A.; Tokunaga, E.; Yamasaki, M.; Shiro, M.; Shibata, N., J. Am. Chem. Soc. 2013, 135,
41 Iodonium Ylide Yang, Y. D.; Azuma, A.; Tokunaga, E.; Yamasaki, M.; Shiro, M.; Shibata, N., J. Am. Chem. Soc. 2013, 135,
42 Comparison of 2 Hypervalent Iodine reagent Yang, Y. D.; Azuma, A.; Tokunaga, E.; Yamasaki, M.; Shiro, M.; Shibata, N., J. Am. Chem. Soc. 2013, 135, Shao, X.; Wang, X.; Yang, T.; Lu, L.; Shen, Q., Angew. Chem. Int. Ed, 2013, 52,
43 Iodonium Ylide Yang, Y. D.; Azuma, A.; Tokunaga, E.; Yamasaki, M.; Shiro, M.; Shibata, N., J. Am. Chem. Soc. 2013, 135,
44 Iodonium Ylide Yang, Y. D.; Azuma, A.; Tokunaga, E.; Yamasaki, M.; Shiro, M.; Shibata, N., J. Am. Chem. Soc. 2013, 135,
45 Iodonium Ylide 46
46 Electrophilic methods Hypervalent iodine reagent can selective introduce SCF 3, but it is potential explosive chemicals. Trifluoromethanesulfenamide, a stable SCF 3 source. Trifluoromethanesulfonyl hypervalent iodonium ylide, can be effectivly applied to enamines, beta-keto esters, indoles. 47
47 Outline 1. Introduction 2. Direct trifluoromethylthiolation Electrophilic trifluoromethylthiolation Transition metal-catalyzed nucleophilic trifluoromethylthiolation 3. Summary 48
48 Transition metal-catalyzed nucleophilic trifluoromethylthiolation R Yield (%) H 55 4-Me 30 4-NO 2 75 Cheap and efficient metal catalyst Stable SCF 3 source Yagupolskii, L, M, Kondratenko, N, V, Sambur, V, P., Synthesis, 1975,
49 Nucleophilic trifluoromethylthiolation Palladium catalyzed nucleophilic method 50 Teverovskiy, G.; Surry, D. S.; Buchwald, S. L., Angew. Chem. Int. Ed 2011, 50,
50 Nucleophilic trifluoromethylthiolation 51 Zhang, C. P.; Vicic, D. A., J. Am. Chem. Soc. 2012, 134,
51 Nucleophilic trifluoromethylthiolation 52 Zhang, C. P.; Vicic, D. A., Chem. Asian J, 2012, 7,
52 Nucleophilic trifluoromethylthiolation From element Sulfur Weng, Z.; He, W.; Chen, C.; Lee, R.; Tan, D.; Lai, Z.; Kong, D.; Yuan, Y.; Huang, K. W., Angew. Chem. Int. Ed, 2013, 52,
53 Nucleophilic trifluoromethylthiolation Weng, Z.; He, W.; Chen, C.; Lee, R.; Tan, D.; Lai, Z.; Kong, D.; Yuan, Y.; Huang, K. W., Angew. Chem. Int. Ed, 2013, 52,
54 Nucleophilic trifluoromethylthiolation Path A Path B 55 Chen, C.; Xie, Y.; Chu, L.; Wang, R. W.; Zhang, X.; Qing, F. L., Angew. Chem. Int. Ed, 2012, 51,
55 Nucleophilic trifluoromethylthiolation 56
56 Nucleophilic trifluoromethylthiolation 57
57 Nucleophilic trifluoromethylthiolation 58 Chen, C.; Xie, Y.; Chu, L.; Wang, R. W.; Zhang, X.; Qing, F. L., Angew. Chem. Int. Ed, 2012, 51,
58 Nucleophilic trifluoromethylthiolation 59 Chen, C.; Chu, L.; Qing, F. L., J. Am. Chem. Soc 2012, 134,
59 Nucleophilic trifluoromethylthiolation Total synthesis of Toltrazuril A. Gunther, K.-H. Mohrmann, M. Stubbe, H. Ziemann (Bayer AG), DE ,
60 Nucleophilic trifluoromethylthiolation Pd catalyst ~ $260/g Ligand ~ $200/g 61 Teverovskiy, G.; Surry, D. S.; Buchwald, S. L., Angew. Chem. Int. Ed 2011, 50,
61 Nucleophilic methods From Palladium to Nickel, then to Copper, to find a cheaper but highly efficient catalyst. Improvement of unstable or inconvient M-SCF 3 source. 62
62 Summary Electrophilic methods Hypervalent Iodine reagent Trifluoromethanesulfenamide Trifluoromethanesulfony hypervalent iodonium ylide Nucleophilic methods Optimize the reaction catalyst. One pot reaction. 63
63 Acknowledgements Dr. Xuefei Huang Group members: Zhaojun, Weizhun, Hovig, Herbert, Qian, Berm, Peng, Mehdi, Jicheng, Bo, Keisuke, Jingguang, Issac, Sherif My friends All your attention 64
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